Poly (2-methyl- N-vinylimidazole) was let to react with n-butyl, n-hexyl, n-octyl and n-dodecyl bromides, respectively. The resulting n-alklyimidazolium bromide polymers, except the butylimidazolium polymer, were insoluble in water when the reaction advanced. But these waterinsoluble polymers became soluble when they were treated with hydrogen bromide. All the polymers were also soluble in methanol and ethanol. It was found that the modified polymers possess higher viscosity and lower surface tension in aqueous solutions than the original polymers. However the introduction of such a long and hydrophobic chain as n-dodecyl group into the polymer chain was found to give rather opposite properties. The results of these experiments were discussed from a standpoint of the molecular shape of the polymer in solution. The subsidence of kaolin suspension by the dodecyl imidazolium bromide polymer was also investigated ; the final sedimentation volume was found to be smaller in proportion to the content of dodecyl groups in the polymer chain, and a clear supernatant solution was obtained without redispersion of the precipitates. Although a quantitative corelation between chain length and the content of alkyl bromides and the properties of imidazolium polymers was not obtained, it was shown that a suitably modified polymer will be useful as a cationic polysoap.
Methods for synthesizing 1, 3-dicyanopropene, which was the starting material for the synthesis of 1, 5-diaminopentane, were studied. β-Hydroxyglutaronitrile was prepared by the reaction between epichlorohydrin and sodium cyanide. The product was acetylated, and after the elimination of acetic acid 1, 3-dicyanopropene was obtained. The overall yield was about 50%. 1, 3-Dicyanopropene was also synthesized by the cyanation of 1, 3-dichloropropene. The yield of 1, 3-dichloropropene by the chlorination of allyl chloride under high temperature was as high as 90%. At low temperature, 1, 2, 3-trichloropropane was produced by additive chlorination of allyl chloride. When 1, 3-dichloropropene was treated with hydrogen cyanide in the presence of calcium carbonate 1-chloro-3-cyanopropene was formed in high yield. The cyanation of 1-chloro-3-cyanopropene into 1, 3-dicyanopropene was rather difficult, but 1, 3-dicyanopropene was obtained by the cyanation of 3-chloro-1-cyanopropene, which arose from the rearrangement of 1-chloro-3-cyanopropene.
The reaction of S-methyl-isothiosemicarbazide hydriodide with morpholine or pyrrolidine gave the corresponding new 1, 1-disubstituted-3-aminoguanidines in good yields, but the yield was poor in the case of piperidine. Therefore the reaction of cyanopiperidine with hydrazine was attempted. This reaction required considerably prolonged reaction time, and the yield was not improved. The reactivity of pyrrolidine, morpholine and piperidine with S-methyl-isothiosemicarbazide to give the corresponding 1, 1-disubstituted-3-aminoguanidines decreased in the order named, whereas the order of reactivity was pyrrolidine>piperidine> morpholine in the case of the reaction with S-methylisothiourea. These results suggest that the reaction mechanism may be somewhat different between these two reactions.
The synthesis of β-propiolactone by the reaction of ketene with formaldehyde was studied. When equimolar amounts of both gaseous starting materials were fed, higher yields of β-propiolactone were obtained. In order to control the reaction conditions, the method of quantitative generation and the analysis of two gaseous starting materials were establishd. β-Propiolactone and acetone were used as the solvents. Anhydrous aluminium chloride containing small amounts of zinc chloride was found to be the best catalyst. This catalyst dissolved easily in acetone. It was confirmed that acetone in the solution changed with time at room temperature to give mesityl oxide, which deactivated the catalyst. This deactivation could be prevented by storing this solution below 0°C. The shorter average residence time of the catalyst gave better yields of β-propiolactone because of fast absorption and chemical reaction rates of two gaseous materials and of the deactivation of the catalyst. Rate-determining step of this reaction was considered to be chemical reaction, and not absorption. The optimum catalyst concentration for the main reaction was determined.
Reactions of 2-alkyl-4, 6-bis (trichloromethyl) -s-triazine with aliphatic amines have been studied. Thus, the method has been established, by which two trichloromethyl groups were selectively replaced by aliphatic amino groups. By this method, a number of 2-alkyl-4, 6-bis (alkylamino) -s-triazines were synthesized in order to determine the effect on nitrification inhibitory and herbicidal activities.